Composition of matter suitable for dyeing



Patented er,

WINFRID HENTRICH; F WIESDORF-ON THE-RHINE, ANTON QSSENBECK, 0F COLOGNE- MULHEIM, AND ERNST TIETZE, OF COLOGNE-ON-THE-RHINE, GERMANY, ASSIGNORS T0 GENERAL ANILINE WORKS, INC., 01 NEW YORK, N. Y., A CORPORATION DELA- WARE COMPOSITION OF MATTER SUITABLE EQR DYEIITG No Drawing. Application 'filed July 30, 1929, Serial No. 382,276, and in Germany'August 3, 1928.

Ihe present invention relates to new compositions of matter suitable for dyeing and printing.

A number of compounds possessing phei 5 nolic of enolic character find extensive apstantive azo dyestuffs on vegetable fibers in I order to render the same fast to washing. More recent representatives of the phenolic series are, in the manufacture of ice colors, the 2.3-hydroxynaphthoic acid arylides or the an alkali salts thereof or in the enolic series, the

diaceto acetyl derivatives of 4.4! -diami nod1- phenyl and homologues thereof.

Insofar as such products were in the state of free phenols or enols, the dyer orprinter 2a was first called upon to bring the sameinto solution by a cumbersome procedure, in most cases with the help of caustic alkalies in which connection it was very often essential that any excess of caustic alkali should be avoided, having regard to the intended application of the product, for example, in coupling dyestuffs on the fiber with the use of diazo compounds sensitive to alkalies.

It is, moreover, known that in the-manu- 9 facture of aqueous solutions of naphtholates,

such as for example, the sodium salt of 2.3- hydroxynaphthoic acid anilide or other arylides of this series or of similar compounds, such as, vfor example, the sodium salts of acetoacetic acid arylide, or on dissolving mixtures of these compounds and other water soluble, neutral or alkaline reacting materials, cloudy solutions filled with flakes are 40 obtained as the result of hydrolysis, due to the slight acidity of the phenolic or enolic hydroxy groups. In order to remedy this disadvantage, it has been necessary in the manufacture of the respective solutions to prevent the hydrolytic clouding by free naphthol and the like by the addition of further quantities of caustic alkali lye.

In accordance with-the present invention, there are obtained compositions of matter in the solid form, which are excellently stable and resistant to air and which dissolve very readily in water without the use of any addition, even without the addition of alkali lye,

yielding withsuitable choice of the relative- .mixture perfectly clear solutions without a harmful excess of alkali. The process of manufacture in accordance with'this invention is by incorporating with a coupling component, containing at least one hydroxy group but being free from a sulfonic or carboxylic acid group, including those compounds of .enolic character or with the alkali compound thereof or with a mixture of these compounds, a small quantity of an alkali starch compond (compare, for example, Journal fiir prak)tische Chemie, vol. 101, p.314 et-seq. 1921 The quantity of the alkali starch com- 1 pound added varies somewhat. When using the coupling component with free hydroxy groups, there are mixed about molecular quantities, that means for each hydroxy group one molecule of the caustic alkali in the form of the alkali starch compound is added. On the other hand, when using the alkali metal salts of the coupling components containing hydroxy groups, only a small quantity of the alkali starch is to be added for preventing the hydrolytic dissociation of the group OMe (Me=alkali metal) of the coupling component. The amount of thedissociation somewhat depends on the specific compound used and on the quantity of the water it is diluted with; therefore the larger the specific dissociation of the compound and the dilution of the aqueous solution prepared, the greater must be the quantity of the alkali starch added for preventing the hydrolytic dissociation.

Otherorganic or inorganic substances may be added to our new compositions, especially a diazo compound, the diazo group of which is blockaded and is set free by the action of an acid. Such compounds are for example,

suitable nitroamines and diazoamino compounds, (compare the copending applications Serial No. 358,153, filed April 25, 1929, and Serial No. 37 7 ,075, filed July 9, 1929, for new diazo amino compounds, and application Ser. No.377,07 6 filed July 9, 1929' for. diazo amino compounds). Those compositions containing besides the alkali starch a diazotizing component, in a blockaded form and in a quantity about equimolec-ular to the coupling component are especially valuable in the ,printing process. lit is to beunderstood that both the mixtures containing the coupling 7 components with free hydroxy groups and the alkali metal salts thereof fall within the scope of our invention.-

In consequence of the above mentioned remarkable properties the mixtures thus obtained with alkali starch can be employed directly without any auxiliary operations for the purpose of dyeing and printing.

The following examples illustrate the in vention without limiting it thereto:

Example 1.100 parts by weight of the dry, finely divided sodium salt of 2.3-hydroxynaphthoic acid o-toluidide (or of 2.3 hydroxy-naphthoic acid-4c-chloro-2-methylanilide)v are intimately mixed with 3- to 8 parts by weight of alkali starch, The mixture, in contradistinction to the compound 01 sonar are intimately mixed with 5 parts by weight of alkah starch. The product thus obtained yields a clear aqueous solution, which even on standing shows no hydrolytic clouding.

'Ewampze 3.100 parts by weight of 2.3- hydroxynaphtho'ic acid anilide are intimately ground with 47 parts by weight of alkali starch. The mixture thus obtained remains unchanged in the air and dissolves to a clear solution in warm water. The solution can therefore be used directly forthe slop-padding of vegetable fibers.

the

Emamp-Ze 4.100 parts by weight of acetolution can be employed directly for developing the aminodiazo dyestuif of the formula H NH ant

obtained from 2-naphthyl amine-5-sulfonic acid, l-amino-5-hydroxynaphthalene-7-sulionic acid and 4-benzoylamino-2-amino-5- hydroxynaphthalene-7-sulfonic acid, after first dyeing and then diazotizing on the fiber. In this manner vivid green'shades are obtained (compare German Patent No. 268792) In an analogous manner the mixture obtainable from l-phenyl-3-methyl-5-pyrazolone and alkali starch can also be used as a developer which is stable in the air and soluble in water. 1

Example 5.-1OO parts by weight of di- (acetoacetyl) -tolidide are treated as in the above example with 64 parts by weight of alkali starch. The powder, which remains unchanged in air dissolves without any addition to a clear solution in water at 50 C.

There can be added to this, for example, suitable nitrosoamines or diazoamino compounds of the kind described, for example, in the copending applications Ser. No. 358153, filed April 25, 1929, Ser. No. 377,075, filed July 9, 1929 for new diazo amino compounds, and Ser. No. 377,076, filed July 9, 1929 for diazo amino compounds. Likewise, any other suitable substances or mixtures of substances of any inorganic or organic nature can be added.

E wample 6. parts by weight of ,8- naphthol are intimately ground with 92 parts by weight of alkali starch. The mixture thus obtained is stable to air and readily soluble in moderately warm water. The solution can be used directly for the development, for example, of the aminoazo dyestufi oi the formula: a I

obtained from aniline and 3-benzoylamino- 2-amino-5-naphthol-7-sulfonic acid, after first dyeing and then diazotizing on the fiber, when vivid reddish orange shades are produced (compare German Patent No, 151,017)

Ewample 7.100 parts of sulby weight fazone v I mixture of the said two compounds and alkali starch are capable of application in an analogous manner to that described in Examples 4 and 6, for example, as developing solutions for fixing substantive azo dyestuffs on the vegetable fiber in order to render the same fast to washing.

We claim:

1. As a new composition of matter a mixture comprising an alkali metal salt of a coupling componentcontaining at least one hydroxy group and being free from sulfonic and carboxylic acid groups, and an alkali starch compound in a quantity necessary for preventing the hydrolytic dissociation of the 4 coupling component in aqueous solution,

ing resistant to air, soluble in Water and having utility in dyeing and printing processes.

2. As a new composition of matter a mixture comprising an alkali metal salt of a coupling component containing at least one hydroxy compound in a? quantity necessary for preventing the hydrolytic dissociation of the group and being free from sulfonic' and carboxylic acid groups, an alkali starch air, soluble in water and havingutility in dyeing and printing processes. a 5.. As a new composition of matters. mixture comprising a 2.3-hydroxynaphthoic acid p-anisidide inform of its sodium salt and an alkali starch compound in a quantity necessaryfor p'reventing the hydrolytic dissociation of the coupling component in aqueous solution, being resistant to air, soluble in water and having utility in dyeing and printing processes.

6. As a new composition of matter a mixture consisting of 30 parts by Weight of the sodium salt of 2.3-hydroxynaphthoic acid panisidide, or parts by weight of alkali starch and 7 0 parts by Weight of the diazoamino compound obtained from diazotized l-chloro-2-anisidine and 4-sulfo-2-aminobenzoic acid, being resistant to air, soluble in water and having utility in dyeing and printing processes.

In testimony-whereof, we aflix our signatures.

VVINFRID HENTRICH. ANTON I OSSENBEGK.

' ERNST TIETZE.

coupling component in aqueous solution, and

a watersoluble'd-iazo-amino compound in a quantity about equivalent to the coupling component, being resistant to air, soluble in water and having utility in dyeing and printing processes. g

3. As a new composition of matter a mixture comprising a 2.3-hydroxynaphthoic acid arylide and an alkali. starch compound in a quantity necessary for preventing 'the hydrolytic dissociation of the coupling component in aqueous solution, being resistant to air, soluble in water and having utility in dyeingsand printing processes.

4:. a new composition of matter a mixture comprising a 2.3-hydroxynaphthoic acid arylide, an alkali starch compound in a quantity necessary for preventing the hydrolytic' 'dlssoclation of the coupling component in aqueous solution, -and a watersoluble diazo amino compound prepared from any diazo- 1 tizing component free from groups inducing solubility in'water and apri-mary amine containing at least one group inducing solubility in water, in a quantity about equivalent to the 'couphng component, being resistant to 

